Conversion of non-fusible and insoluble polyacroleins with hydroxyl amine



United States Patent Oil ice 3,234,164

Patented Feb. 8, 1966 3 3 164 spontaneous or radical polymerization under the hetero- T 1 Y m i geneous reaction conditions required. That is, the polyacrolein at theheginning of the reaction is present in wemer Kern aim, Dim Schweitzer gonigstein solid undissolved form and only the resulting derivative Taunus i R015: s g Maia; p a 5 goes into solution as the reaction proceeds. The polymany, assignors to Deutsche Goldnd Silber. acrolein oximes which are formed form water soluble Scheideanstalt vormais Roessler, Frankfurt am alkali metal salts which can be precipitated by acidfica- Main, Germany No Drawing. Filed June 12, 1962, Ser. No. 201,756 Claims priority, application Germany, Mar. 23, 1955,

tion as they are capable of forming specific metal salts that can be used as specific ion exchange agents.

The reactions according to the invention can be car- D g s ggfg gf l0 ried out at room temperature but moderately raised temperatures expedite the reactions. Temperatures over 150 The present invention relates to a process for the treat- C. can engender side reactions which may cause the rement of non-fusible homopolymers of acrolein which conaction product to lose its stability. Forconvenience, it rain substantially no free aldehyde groups and which are is preferable to employ temperature not over the normal normally insoluble in normal or anic solvents to convert boiling point of the aqueous solutions preferably emthem into more valuable products and especially prodployed for the reaction. ucts which are soluble in a number of solvents. In the reactions according to the invention the poly- It is known that unstabilized acrolein spontaneously acroleins employed are not degraded to form monomeric polymerizes upon standing to produce a solid, non-fusiacrolein and therefore the polyacroleins do not serve as ble and insoluble product which has been designated as a source of monomeric acrolein. disacryl. (Redtenbacher, Liebigs Ann. Chem. 47 The oxime derivatives of polyacrolein obtained ac- (1843), p. 113.) Acrolein furthermore polymerizes uncording to the invention in addition to being useful as der the influence of radical forming catalysts to produce ion exchange agents can also be used as wash primers for infusible polymers which are insoluble in the known orthe surface treatment of textiles, skins and leather. ganic solvents. It therefore was previously assumed that The following examples will serve to illustrate several hardly any double bonds'or aldehyde groups were reembodiments of the invention: tained in such polymers and that therefore the polyacroleins are unsuited for the production of polyaldehydes Example 1 (Houben-Weyl, vol. VII, pages 133-135). It was only in certain oligomers of acrolein (Gilbert, Donleavy, J. Amer. Chem. Soc. 60 (1938), p. 1911) that certain copolymers of acrolein with other vinyl compounds that reactive aldehyde groups could be ascertained. The homopolymers of acrolein were previously considered rather unreactive and achieved no technical significance (Schi'ldknecht, Vinyl and Related Polymers, Wiley and Sons, New York, 1952, page 760).

1 gram of polyacrolein obtained by spontaneous polymerization was suspended in a solution of 2 grams of hydroxylamine hydrochloride in 50 cc. of N aqueous sodium hydroxide and the suspension shaken at room temperature for 24 hours. The resulting mixture was then heated for 12 hours at 50 C. and the small uantities q a of undissolved material were removed from the solution. Upon acidification of the solution with 2 N acetic acid, a yellowish product was precipitated which in damp state Accordin to the invention it was unexpectedly (115- 1 bl s i on do hdroxd. Aftr covered that the homopolymers of acrolein contrary to 40 2;? i so i 1 m y 1 e prior indications do contain aldehyde groups but that is 0 repreclpltanon Its mtrogen Content was these are in the form of aldehyde-hydrate-ether group- Example 2 ings and therefore not free and that the intermolecular ether groupin s are the cause of the cross-linking and Of an Polymer Qbtamed Y P l therefore their infusibility and insolubility, as indicated BYE-321011 of 3111918! 111 Presencfi Of l K01! fedOX in the following formula: catalyst in aqueous solution was shaken during 24 hours CII CHC1I CHCH CHCII2?H-CllrCHCH -CII.

cg /GE\ /CH CH Hn-oH 11 o O on n/o 0 no on JHCH CHCHgJH Furthermore, according to the invention it was found at room temperature with a solution of 1 gram hydroxylaunexpectedly that these masked aldehyde groups which mine hydrochloride in 25 cc. of 2 aqueous NaOI-I. are present in all such macromolecular homopolymers 59 The mixture was then treated as described in Example 1.

of acrolein which are infusible and normally insoluble We claim:

in all common organic solvents and which are produced 1. A method of rendering a macromolecular infu-sible, by spontaneous or radical polymerization using radical insoluble homopolymer of acrolein devoid of free aldeforming catalysts such as redox systems and are macrohyde groups selected from the group consisting of polymolecular, having molecular weights above 10,000 (see acroleins produced by spontaneous polymerization and Staudinger, Makromolekulare Chemie & Biologic, page polyacroleins produced by radical polymerization soluble 4, 1947, Basel), can be caused to react with hydroxyl in aqueous sodium hydroxide which comprises reacting amine COmPOUHdS, Preferably y y amine Salts 511th such homopolymer with hydroxyl-amine in an aqueous as hydroxyl amine hydrochloride or sulfate in the pres 31 11 mgdiunL ence of an alkali in an aqueous medium to form oximes.

It was surprising that it is possible to react the infusible, insoluble homopolymers of acrolein obtained by (R f on faugvying page) 2. A polyacrolein oxime produced according to claim 1.

References Cited by the Examiner UNITED STATES PATENTS Finlayson et a1 260-72 Miller et a1 26967 Hartough et a1. 26072 Blanchette et a1. 260-67 Marks 26067 FOREIGN PATENTS 7/1956 Great Britain.

OTHER REFERENCES English Translation of Kunststofle, v01. 53, July 1963, pages 4-24436; pages 11-21.

WILLIAM H. SHORT, Primary Examiner. J. R. LIBERMAN, Examiner. 

1. A METHOD OF RENDERING A MACROMOLECULAR INFUSIBLE, INSOLUBLE HOMOPOLYMER OF ACROLEIN DEVOID OF FREE ALDEHYDE GROUPS SELECTED FROM THE GROUP CONSISTING OF POLYACROLEINS PRODUCED BY SPONTANEOUS POLYMERIZATION AND POLYACROLEINS PRODUCED BY RADICAL POLYMERIZATION SOLUBLE IN AQUEOUS SODIUM HYDROXIDE WHICH COMPRISES REACTING SUCH HOMOPOLYMER WITH HYDROXYLAMINE IN AN AQUEOUS ALKALINE MEDIUM.
 2. A POLYACROLEIN OXIME PRODUCED ACCORDING TO CLAIM
 1. 